Nitroenamine derivatives as pesticides.
Abstract
Novel nitroenamine derivatives of the formula I <IMAGE> in which R1 is hydrogen, C1-C6-alkyl or C3-C6-cycloalkyl, R2 is hydrogen or C1-C6-alkyl, R3 is hydrogen, C1-C6-alkyl or C3-C6-cycloalkyl, R4 is hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl or a radical -CH2-B, or R3 and R4 together are -(CH2)4- or -(CH2)5-; X is halogen or C1-C6-haloalkyl; Y and Z are halogen; A is an aromatic or non-aromatic monocyclic or bicyclic heterocyclic radical which is unsubstituted or mono- to tetrasubstituted, wherein one or two substituents belong to the group comprising C1-C3-haloalkyl, cyclopropyl, halocyclopropyl, C2-C3-alkenyl, C2-C3-alkynyl, C2-C3-haloalkenyl, C2-C3-haloalkynyl, C1-C3-haloalkoxy, C1-C3-alkylthio, C1-C3-haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro and one to four substituents belong to the group comprising C1-C3-alkyl, C1-C3-alkoxy and halogen; B is phenyl, cyanophenyl, nitrophenyl, halophenyl having 1 to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, 5-thiazolyl which is substituted by one to two substituents from the group comprising C1-C3-alkyl, C1-C3-haloalkyl, cyclopropyl, halocyclopropyl, C2-C3-alkenyl, C2-C3-alkynyl, C1-C3-alkoxy, C2-C3-haloalkenyl, C2-C3-haloalkynyl, C1-C3-haloalkoxy, C1-C3-alkylthio, C1-C3-haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro; or 3-pyridyl which is substituted by one to two radicals from the group comprising C1-C3-haloalkyl, cyclopropyl, halocyclopropyl, C2-C3-alkenyl, C2-C3-alkynyl, C2-C3-haloalkenyl, C2-C3-haloalkynyl, C1-C3-haloalkoxy, C1-C3-alkylthio, C1-C3-haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, or 3-pyridyl which is substituted by one to four radicals from the group comprising C1-C3-alkyl, C1-C3-alkoxy or halogen, and their salts with inorganic acids, but only one of the radicals R1, R3 and R4 can represent hydrogen, and their salts can be used as pesticides. Insects and arachnids can preferably be controlled.

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Projected expiry passed 27 March 2011, 15.5 years ago.
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39 claims: 39 independent, 0 dependent
- 1Compound of formula 1whereinR1 Hydrogen, C1-C6-Alkyl or C3-C6Cycloalkyl,R2 Hydrogen or C1-C6-Alkyl,R3 Hydrogen, C1-C6-Alkyl or C3-C6Cycloalkyl,R4 Hydrogen, C1-C6-Alkyl, C3-C6-Cycloalkyl or a residue-CH2-B, or R4 and R4 together - (CH2)4-or - (CH2)5-;X halogen or C1-C6-Haloalkyl;Y and Z halogen;A is an unsubstituted or mono- to tetrasubstituted aromatic or non-aromatic, monocyclic or bicyclic heterocyclic radical, in which one or two substituents from group C1-C3-Haloalkyl, cyclopropyl, halocyclopropyl, C2-C3Alkenyl, C2-C3Alkynyl, C2-C3-Halogenalkenyl, C2-C3-Haloalkynyl, C1-C3-Haloalkoxy, C1-C3-Alkylthio, C1-C3-Halogenalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro and one to four substituents from group C1-C3-Alkyl, Cl-C3-Alkoxy and halogen belong;B phenyl, cyanophenyl, nitrophenyl, halophenyl with 1 to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, by one or two substituents from group C1-C3-Alkyl, C1-C3-Haloalkyl, cyclopropyl, halocyclopropyl, C2-C3Alkenyl, C2-C3Alkynyl, C1-C3-Alkoxy, C2-C3-Halogenalkenyl, C2-C3-Haloalkynyl, C1-C3-Haloalkoxy, C1-C3-Alkylthio, C1-C3Haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro substituted 5-thiazolyl;or by one or two radicals from group C1-C3-Halogenalkyl, cyclopropyl, halocydopropyl, C2-C3Alkenyl, C2-C3Alkynyl, CrC.3-Halogenalkenyl, C2-C3-Haloalkynyl, C1-C3-Haloalkoxy, C1-C3-Alkylthio, C1-C3-Halogenalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyan and nitro or by one to four radicals from group C1-C3-Alkyl, C1-C3-Alkoxy or halogen substituted 3-pyridyl, and their salts with inorganic acids;where only one of the radicals R1, R3 and R4 can stand for hydrogen. 1. Verbindung der Formel 1 worin R1 Wasserstoff, C1-C6-Alkyl oder C3-C6-Cycloalkyl,R2 Wasserstoff oder C1-C6-Alkyl,R3 Wasserstoff, C1-C6-Alkyl oder C3-C6-Cycloalkyl,R4 Wasserstoff, C1-C6-Alkyl, C3-C6-Cycloalkyl oder einen Rest-CH2-B, oder R4 und R4 gemeinsam -(CH2)4-oder -(CH2)5-;X Halogen oder C1-C6-Haloalkyl;Y und Z Halogen;A einen unsubstituierten oder ein- bis vierfach substituierten aromatischen oder nicht-aromatischen, monocyclischen oder bicyclischen heterocyclischen Rest, worin ein oder zwei Substituenten der Gruppe C1-C3-Halogenalkyl, Cyclopropyl, Halogencyclopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, C2-C3-Halogenalkenyl, C2-C3-Halogenalkinyl, C1-C3-Halogenalkoxy, C1-C3-Alkylthio, C1-C3-Halogenalkylthio, Allyloxy, Propargyloxy, Allylthio, Propargylthio, Halogenallyloxy, Halogenallylthio, Cyan und Nitro und ein bis vier Substituenten der Gruppe C1-C3-Alkyl, Cl-C3-Alkoxy und Halogen angehören;B Phenyl, Cyanophenyl, Nitrophenyl, Halogenphenyl mit 1 bis 3 Halogenatomen, 3-Pyridyl, 5-Thiazolyl, durch ein bis zwei Substituenten aus der Gruppe C1-C3-Alkyl, C1-C3-Halogenalkyl, Cyclopropyl, Halogencyclopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, C1-C3-Alkoxy, C2-C3-Halogenalkenyl, C2-C3-Halogenalkinyl, C1-C3-Halogenalkoxy, C1-C3-Alkylthio, C1-C3-Halogenalkylthio, Allyloxy, Propargyloxy, Allylthio, Propargylthio, Halogenallyloxy, Halogenallylthio, Halogen, Cyan und Nitro substituiertes 5-Thiazolyl;oder durch ein bis zwei Reste aus der Gruppe C1-C3-Halogenalkyl, Cyclopropyl, Halogencydopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, CrC3-Halogenalkenyl, C2-C3-Halogenalkinyl, C1-C3-Halogenalkoxy, C1-C3-Alkylthio, C1-C3-Halogenalkylthio, Allyloxy, Propargyloxy, Allylthio, Propargylthio, Halogenallyloxy, Halogenallylthio, Cyan und Nitro oder durch ein bis vier Reste aus der Gruppe C1-C3-Alkyl, C1-C3-Alkoxy oder Halogen substituiertes 3-Pyridyl bedeuten, sowie deren Salze mit anorganischen Säuren;wobei nur einer der Reste R1, R3 und R4 für Wasserstoff stehen kann. 1. Verfahren zur Herstellung einer Verbindung der Formel I worin R1 Wasserstoff, C1-C6-Alkyl oder C3-C6-Cycloalkyl,R2 Wasserstoff oder C1-C6-Alkyl,R3 Wasserstoff, C1-C6-Alkyl oder C3-C6-Cydoalkyl,R4 Wasserstoff, C1-C6-Alkyl, C3-C6-Cycloalkyl oder einen Rest -CH2-B, oderR3 und R4 gemeinsam -(CH2)4- oder-(CH2)5-;X Halogen oder C1-C6-Haloalkyl;Y und Z Halogen;Aeinen unsubstituierten oder ein- bis vierfach substituierten aromatischen oder nicht-aromatischen, monocyclischen oder bicyclischen heterocyclischen Rest, worin ein oder zwei Substituenten der Gruppe C1-C3-Halogenalkyl, Cyclopropyl, Halogencyclopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, C2-C3-Halogenalkenyl, C2-C3-Halogenalkinyl, C1-C3-Halogenalkoxy, C1-C3-Alkylthio, C1-C3-Halogenalkylthio, Allyloxy, Propargyloxy, Allylthio, Propargylthio, Halogenallyloxy, Halogenallylthio, Cyan und Nitro und ein bis vier Substituenten der Gruppe C1-C3-Alkyl, C1-C3-Alkoxy und Halogen angehören;B Phenyl, Cyanophenyl, Nitrophenyl, Halogenphenyl mit 1 bis 3 Halogenatomen, 3-Pyridyl, 5-Thiazolyl, durch ein bis zwei Substituenten aus der Gruppe C1-C3-Alkyl, Cl-C3-Halogenalkyl, Cyclopropyl, Halogencyclopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, C1-C3-Alkoxy, C2-C3-Halogenalkenyl, C2-C3-Halogenalkinyl, Ci-C3-Halogenalkoxy, C1-C3-Alkylthio, C1-C3-Halogenalkylthio, Allyloxy, Propargyloxy, Allylthio, Propargylthio, Halogenallyloxy, Halogenallylthio, Halogen, Cyan und Nitro substituiertes 5-Thiazolyl;oder durch ein bis zwei Reste aus der Gruppe C1-C3-Halogenalkyl, Cyclopropyl, Halogencyclopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, C2-C3-Halogenalkenyl, C2-C3-Halogenalkinyl, C1-C3-Halogenalkoxy, C1-C3-Alkylthio, C1-C3-Halogenalkylthio, Allyloxy, Propargyloxy, Allylthio, Propargylthio, Halogenallyloxy, Halogenallylthio, Cyan und Nitro oder durch ein bis vier Reste aus der Gruppe C1-C3-Alkyl, Cl-C3-Alkoxy oder Halogen substituiertes 3-Pyridyl bedeuten, sowie deren Salze mit anorganischen Säuren;wobei nur einer der Reste R1, R3 und R4 für Wasserstoff stehen kanndadurch gekennzeichnet, dass man eine Verbindung der Formel II mit einer Verbindung der Formel 111 unter pH-neutralen Reaktionsbedingungen umsetzt, wobei R1 bis R4, A, X, Y und Z die oben angegebenen Bedeutungen haben.
- 2Verbindung der Formel gemäss Anspruch 1, dadurch gekennzeichnet, dass der heterocyclische Rest A ungesättigt ist und über eines seiner Ring-Kohlenstoffatome an den Rest der Verbindung der Formel gebunden ist. 2. Verfahren zur Herstellung einer Verbindung der Formel I gemäss Anspruch 1, dadurch gekennzeichnet, dass der heterocyclische Rest A ungesättigt ist und über eines seiner Ring-Kohlenstoffatome an den Rest der Verbindung der Formel 1 gebunden ist 2nd Compound of the formula according to claim 1, characterized in that the heterocyclic radical A is unsaturated and is bonded via one of its ring carbon atoms to the rest of the compound of the formula.
- 3Verbindung der Formel gemäss Anspruch 2, dadurch gekennzeichnet, dass der heterocyclische Rest A mindestens ein Stickstoffatom enthält. 3. Verfahren zur Herstellung einer Verbindung der Formel gemäss Anspruch 2, dadurch gekennzeichnet, dass der heterocyclische Rest A mindestens ein Stickstoffatom enthält. 3rd Compound of the formula according to claim 2, characterized in that the heterocyclic radical A contains at least one nitrogen atom.
- 4Verbindung der Formel I gemäss Anspruch 2, dadurch gekennzeichnet, dass der heterocyclische Rest A ein bis drei Heteroatome aus der Reihe Sauerstoff, Schwefel und Stickstoff enthält, von denen höchstens eines Sauerstoff- oder Schwefelatom ist. 4. Verfahren zur Herstellung einer Verbindung der Formel gemäss Anspruch 2, dadurch gekennzeichnet, dass der heterocyclische RestA ein bis drei Heteroatome aus der Reihe Sauerstoff, Schwefel und Stickstoff enthält, von denen höchstens eines Sauerstoff- oder Schwefelatom ist. 4th Compound of formula I according to claim 2, characterized in that the heterocyclic radical A contains one to three heteroatoms from the series oxygen, sulfur and nitrogen, of which at most one is an oxygen or sulfur atom.
- 5Compound of formula I according to claim 2, characterized in that the heterocyclic radical A is a main body from the grouprepresents which is unsubstituted or, depending on the substitution possibilities of the ring system in question, carries up to four of the substituents defined in claim 1, where E is for C1-C3-Alkyl and Y for hydrogen, C1-C3-Alkyl or cyclopropyl are available. 5. Verbindung der Formel I gemäss Anspruch 2, dadurch gekennzeichnet, dass der heterocyclische Rest A einen Grundkörper aus der Gruppe darstellt, welcher unsubstituiert ist oder je nach den Substitutionsmöglichkeiten des betreffenden Ringsystems bis zu vier der im Anspruch 1 definierten Substituenten trägt, wobei E für C1-C3-Alkyl und Y für Wasserstoff, C1-C3-Alkyl oder Cyclopropyl stehen. 5. Verfahren zur Herstellung einer Verbindung der Formel gemäss Anspruch 2, dadurch gekennzeichnet, dass der heterocyclische Rest A einen Grundkörper aus der Gruppe darstellt, welcher unsubstituiert ist oder je nach den Substitutionsmöglichkeiten des betreffenden Ringsystems bis zu vier der im Anspruch 1 definierten Substituenten trägt, wobei E für C1-C3-Alkyl und Y für Wasserstoff, C1-C3-Alkyl oder Cyclopropyl stehen.
- 6Compound of the formula according to one of claims 1 to 5, characterized in that the heterocyclic radicals A are unsubstituted or one to three substituents from the group halogen, C1-C3-Alkyl, C1-C3Haloalkyl, C1-C3-Haloalkoxy or C1-C3- Wear alkoxy. 6. Verbindung der Formel gemäss einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die heterocyclischen Reste A unsubstituiert sind oder ein bis drei Substituenten aus der Gruppe Halogen, C1-C3-Alkyl, C1-C3-Halogenalkyl, C1-C3-Halogenalkoxy oder C1-C3-Alkoxy tragen. 6. Verfahren zur Herstellung einer Verbindung der Formel I gemäss einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die heterocyclischen Reste A unsubstituiert sind oder ein bis drei Substituenten aus der Gruppe Halogen, C1-C3-Alkyl, C1-C3-Halogenalkyl, C1-C3-Halogenalkoxy oder C1-C3-Alkoxy tragen.
- 7Compound of the formula according to claim 6, characterized in that the heterocyclic radicals A are pyridyl radicals or thiazolyl radicals. 7. Verbindung der Formel gemäss Anspruch 6, dadurch gekennzeichnet, dass die heterocyclischen Reste A Pyridylreste oder Thiazolylreste sind. 7. Verfahren zur Herstellung einer Verbindung der Formel gemäss Anspruch 6, dadurch gekennzeichnet, dass die heterocyclischen Reste A Pyridylreste oder Thiazolylreste sind.
- 8Verbindung der Formel I gemäss Anspruch 7, dadurch gekennzeichnet, dass A für 3-Pyridyl, 2-Halogen- pyrid-5-yl, 2,3-Dihalogenpyrid-5-yl oder2-Halogenthiazol-4-yl, 1-Oxopyrid-3-yl, 1-Oxo-2-halogenpyrid-5-yl oder 1-Oxo-2,3-dihalogenpyrid-5-yl steht. 8. Verfahren zur Herstellung einer Verbindung der Formel 1 gemäss Anspruch 7, dadurch gekennzeichnet, dass A für 3-Pyridyl, 2-Halogenpyrid-5-yl, 2,3-Dihalogenpyrid-5-yl oder 2-Halogenthiazol-4-yl, 1-Oxopyrid-3-yl, 1-Oxo-2-hatogenpyrid-5-yl oder 1-Oxo-2,3-dihalogenpyrid-5-yl steht. 8th. Compound of formula I according to claim 7, characterized in that A is 3-pyridyl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl or 2-halothiazol-4-yl, 1-oxopyrid-3 -yl, 1-oxo-2-halopyrid-5-yl or 1-oxo-2,3-dihalopyrid-5-yl.
- 9Compound of the formula according to claim 1, characterized in that the radical B represents a phenyl, pyridyl or thiazolyl radical which is unsubstituted or by one or two radicals from the group halogen, C1-C3-Alkyl, C1-C3Haloalkyl, C1-C3-Haloalkoxy or C1-C3Alkoxy is substituted. 9. Verbindung der Formel gemäss Anspruch 1, dadurch gekennzeichnet, dass der Rest B für einen Phenyl-, Pyridyl- oder Thiazolylrest steht, welcher unsubstituiert oder durch ein bis zwei Reste aus der Gruppe Halogen, C1-C3-Alkyl, C1-C3-Halogenalkyl, C1-C3-Halogenalkoxy oder C1-C3-Alkoxy substituiert ist. 9. Verfahren zur Herstellung einer Verbindung der Formel gemäss Anspruch 1, dadurch gekennzeichnet, dass der Rest B für einen Phenyl-, Pyridyl- oder Thiazolylrest steht, welcher unsubstituiert oder durch ein bis zwei Reste aus der Gruppe Halogen, C1-C3-Alkyl, C1-C3-Halogenalkyl, C1-C3-Halogenalkoxy oder C1-C3-Alkoxy substituiert ist.
- 10Verbindung der Formel 1 gemäss Anspruch 1, dadurch gekennzeichnet, dass R1 und R3 Wasserstoff, Methyl, Äthyl oder Cyclopropyl bedeuten. 10. Verfahren zur Herstellung einer Verbindung der Formel 1 gemäss Anspruch 1, dadurch gekennzeichnet, dass R1 und R3 Wasserstoff, Methyl, Äthyl oder Cyclopropyl bedeuten. 10th Compound of formula 1 according to claim 1, characterized in that R1 and R3 Is hydrogen, methyl, ethyl or cyclopropyl.
- 11Compound of the formula according to claim 1, characterized in that R2 Means hydrogen. 11. Verbindung der Formel gemäss Anspruch 1, dadurch gekennzeichnet, dass R2 Wasserstoff bedeutet. 11. Verfahren zur Herstellung einer Verbindung der Formel I gemäss Anspruch 1, dadurch gekennzeichnet, dass R2 Wasserstoff bedeutet.
- 12Verbindung der Formel gemäss Anspruch 1, dadurch gekennzeichnet, dass R4 Wasserstoff oder Methyl bedeutet 12. Verfahren zur Herstellung einer Verbindung der Formel gemäss Anspruch 1, dadurch gekennzeichnet, dass R4 Wasserstoff oder Methyl bedeutet. 12th Compound of the formula according to claim 1, characterized in that R4 Means hydrogen or methyl
- 13Compound of formula I according to claim 1, characterized in that R1 and R3 independently of one another hydrogen, methyl, ethyl or cyclopropyl, R2 Hydrogen, R4 Hydrogen or methyl, A pyridyl, 1-oxopyridyl, thiazolyl or in each case by one to three substituents from the group halogen, C1-C3-Alkyl, C1-C3Haloalkyl, C1-C3-Haloalkoxy or C1-C3Alkoxy substituted pyridyl, 1-oxopyridyl or thiazolyl mean. 13. Verbindung der Formel I gemäss Anspruch 1, dadurch gekennzeichnet, dass R1 und R3 unabhängig voneinander Wasserstoff, Methyl, Äthyl oder Cyclopropyl, R2 Wasserstoff, R4 Wasserstoff oder Methyl, A Pyridyl, 1-Oxopyridyl, Thiazolyl oder jeweils durch ein bis drei Substituenten aus der Gruppe Halogen, C1-C3-Alkyl, C1-C3-Halogenalkyl, C1-C3-Halogenalkoxy oder C1-C3-Alkoxy substituiertes Pyridyl, 1-Oxopyridyl oder Thiazolyl bedeuten. 13. Verfahren zur Herstellung einer Verbindung der Formel 1 gemäss Anspruch 1, dadurch gekennzeichnet, dass R1 und R3 unabhängig voneinander Wasserstoff, Methyl, Äthyl oder Cyclopropyl, R2 Wasserstoff, R4 Wasserstoff oder Methyl, A Pyridyl, 1-Oxopyridyl, Thiazolyl oder jeweils durch ein bis drei Substituenten aus der Gruppe Halogen, C1-C3-Alkyl, Cl-C3-Halogenalkyl, C1-C3-Halogenalkoxy oder C1-C3-Alkoxy substituiertes Pyridyl, 1-Oxopyridyl oder Thiazolyl bedeuten.
- 14Compound of the formula according to one of Claims 1 to 13, characterized in that X is fluorine, chlorine, bromine or C1-C3-Haloalkyl with 1 to 7 fluorine atoms and Y and Z independently of one another are fluorine, chlorine or bromine. 14. Verbindung der Formel gemäss einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass X Fluor, Chlor, Brom oder C1-C3-Haloalkyl mit 1 bis 7 Fluoratomen und Y und Z unabhängig voneinander Fluor, Chlor oder Brom bedeuten. 14. Verfahren zur Herstellung einer Verbindung der Formel I gemäss einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass X Fluor, Chlor, Brom oderC1-C3-Haloalkyl mit 1 bis 7 Fluoratomen und Y und Z unabhängig voneinander Fluor, Chlor oder Brom bedeuten.
- 15Compound of the formula according to one of claims 1 to 13, characterized in that X, Y and Z independently of one another are fluorine, chlorine or bromine. 15. Verbindung der Formel gemäss einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass X, Y und Z unabhängig voneinander Fluor, Chlor oder Brom bedeuten. 15. Verfahren zur Herstellung einer Verbindung der Formel gemäss einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass X, Y und Z unabhängig voneinander Fluor, Chlor oder Brom bedeuten.
- 16Compound of formula I according to claim 15, characterized in that X, Y and Z are chlorine. 16. Verbindung der Formel I gemäss Anspruch 15, dadurch gekennzeichnet, dass X, Y und Z Chlor bedeuten. 16. Verfahren zur Herstellung einer Verbindung der Formel gemäss Anspruch 15, dadurch gekennzeichnet, dass X, Y und Z Chlor bedeuten.
- 17Verbindung der Formel gemäss Anspruch 13, dadurch gekennzeichnet, dass R1 und R3 Methyl;R2 und R4 Wasserstoff;und X, Y und Z unabhängig voneinander Fluor, Chlor oder Brom bedeuten. 17. Verfahren zur Herstellung einer Verbindung der Formel gemäss Anspruch 13, dadurch gekennzeichnet, dass R1 und R3 Methyl;R2 und R4 Wasserstoff;undX, Y und Z unabhängig voneinander Fluor, Chlor oder Brom bedeuten. 17th Compound of the formula according to claim 13, characterized in that R1 and R3 Methyl;R2 and R4 Hydrogen;and X, Y and Z are independently fluorine, chlorine or bromine.
- 18Verbindung der Formel 1 gemäss einem der Ansprüche 13 bis 17, dadurch gekennzeichnet, dass A Pyridyl oder durch ein oder zwei Chloratome substituiertes Pyridyl bedeutet. 18. Verfahren zur Herstellung einer Verbindung der Formel I gemäss einem derAnsprüche 13 bis 17, dadurch gekennzeichnet, dass A Pyridyl oder durch ein oder zwei Chloratome substituiertes Pyridyl bedeutet. 18th Compound of formula 1 according to one of claims 13 to 17, characterized in that A is pyridyl or pyridyl substituted by one or two chlorine atoms.
- 19Verbindung gemäss Anspruch 15, dadurch gekennzeichnet, dass X Fluor oder Brom, Y und Z Halogen bedeuten. 19. Verfahren zur Herstellung einer Verbindung gemäss Anspruch 15, dadurch gekennzeichnet, dass X Fluor oder Brom, Y und Z Halogen bedeuten. 19th Compound according to claim 15, characterized in that X is fluorine or bromine, Y and Z are halogen.
- 20Verbindung gemäss Anspruch 19, dadurch gekennzeichnet, dass X Fluor, Y und Z Fluor oder Chlor bedeuten. 20. Verfahren zur Herstellung einer Verbindung gemäss Anspruch 19, dadurch gekennzeichnet, dass X Fluor, Y und Z Fluor oder Chlor bedeuten. 20th Compound according to claim 19, characterized in that X is fluorine, Y and Z are fluorine or chlorine.
- 21Compound according to claim 14, characterized in that XC1-C6-Halogenalkyl means 4 to 13 halogen atoms. 21. Verbindung gemäss Anspruch 14, dadurch gekennzeichnet, dass X C1-C6-Halogenalkyl mit 4 bis 13 Halogenatomen bedeutet. 21. Verfahren zur Herstellung einer Verbindung gemäss Anspruch 14, dadurch gekennzeichnet, dass X C1-C6-Halogenalkyl mit 4 bis 13 Halogenatomen bedeutet.
- 22Compound according to claim 21, characterized in that XC1-C6-Halogenalkyl means 2 to 13 halogen atoms. 22. Verbindung gemäss Anspruch 21, dadurch gekennzeichnet, dass X C1-C6-Halogenalkyl mit 2 bis 13 Halogenatomen bedeutet. 22. Verfahren zur Herstellung einer Verbindung gemäss Anspruch 21, dadurch gekennzeichnet, dass X Ci-C6-Halogenalkyl mit 2 bis 13 Halogenatomen bedeutet.
- 23A compound according to claim 14, characterized in that X is trifluoromethyl. 23. Verbindung gemäss Anspruch 14, dadurch gekennzeichnet, dass X Trifluormethyl bedeutet. 23. Verfahren zur Herstellung einer Verbindung gemäss Anspruch 14, dadurch gekennzeichnet, dass X Trifluormethyl bedeutet.
- 24Verbindung gemäss Anspruch 14, dadurch gekennzeichnet, dass X einen Rest -C2F5 oder - C3F7 bedeutet. 24. Verfahren zur Herstellung einer Verbindung gemäss Anspruch 14, dadurch gekennzeichnet, dass X einen Rest -C2F5 oder - C3F7, bedeutet. 24th A compound according to claim 14, characterized in that X is a radical -C2F5 or - C3F7 means.
- 25Verbindung der Formel 1 gemäss einem der Ansprüche 13 bis 24, dadurch gekennzeichnet, dass A Thiazolyl oder durch ein Chloratom substituiertes Thiazolyl, vorzugsweise 1,3-Thiazol-5-yl, bedeutet. 25. Verfahren zur Herstellung einer Verbindung der Formel gemäss einem der Ansprüche 13 bis 24, dadurch gekennzeichnet, dass A Thiazolyl oder durch ein Chloratom substituiertes Thiazolyl, vorzugsweise 1,3-Thiazol-5-yl, bedeutet 25th Compound of formula 1 according to any one of claims 13 to 24, characterized in that A is thiazolyl or thiazolyl substituted by a chlorine atom, preferably 1,3-thiazol-5-yl.
- 26A compound according to claim 16 of the formula 26. Verbindung gemäss Anspruch 16 der Formel 26. Verfahren gemäss Anspruch 16 zur Herstellung der Verbindung der Formel
- 2727 A compound according to claim 16 of the formula 27. Verbindung gemäss Anspruch 16 der Formel 27. Verfahren gemäss Anspruch 16 zur Herstellung der Verbindung der Formel
- 2828 A compound according to claim 16 of the formula 28. Verbindung gemäss Anspruch 16 der Formel 28. Verfahren gemäss Anspruch 16 zur Herstellung der Verbindung der Formel
- 29A compound according to claim 16 of the formula 29. Verbindung gemäss Anspruch 16 der Formel 29. Verfahren gemäss Anspruch 16 zur Herstellung der Verbindung der Formel
- 30Verbindung gemäss Anspruch 16 der Formel 30. Verfahren gemäss Anspruch 16 zur Herstellung der Verbindung der Formel 30th A compound according to claim 16 of the formula
- 3131 Compound of formula I according to claim 13, selected from the groupand 31. Verbindung der Formel I gemäss Anspruch 13, ausgewählt aus der Gruppe und 31. Verfahren der Formel I gemäss Anspruch 13, zur Herstellung einer Verbindung, ausgewählt aus der Gruppe und
- 32A process for the preparation of a compound of formula I according to claim 1characterized in that a compound of formula IIwith a compound of formula IIIunder pH-neutral reaction conditions, where R1 to R4, A, X, Y and Z have the meanings given in claim 1. 32. Mittel zur Bekämpfung von Schädlingen, welches neben inerten Zusätzen und Formulierungshilfsmitteln als aktive Komponente eine pestizid wirksame Menge einer Verbindung der Formel 1 gemäss Anspruch 1 enthält. 32. Verfahren zur Herstellung einer Verbindung der Formel I gemäss Anspruch 1 dadurch gekennzeichnet, dass man eine Verbindung der Formel II mit einer Verbindung der Formel III unter pH-neutralen Reaktionsbedingungen umsetzt, wobei R1 bis R4, A, X, Y und Z die in Anspruch 1 angegebenen Bedeutungen haben.
- 33Pesticide composition which, in addition to inert additives and formulation auxiliaries, contains as active component a pesticidally effective amount of a compound of the formula according to claim 1. 33. Mittel zur Bekämpfung von Schädlingen, welches neben inerten Zusätzen und Formulierungshilfsmitteln als aktive Komponente eine pestizid wirksame Menge einer Verbindung der Formel gemäss Anspruch 1 enthält. 33. Verwendung einer Verbindung gemäss Anspruch 1 zur Bekämpfung von Insekten und Vertretem der Ordnung Akarina an Tieren und Pflanzen.
- 34Use of a compound according to claim 1 for controlling insects and representatives of the order Akarina on animals and plants. 34. Verwendung einer Verbindung gemäss Anspruch 1 zur Bekämpfung von Insekten und Vertretern der Ordnung Akarina an Tieren und Pflanzen. 34. Verwendung gemäss Anspruch 33 zur Bekämpfung von pflanzenschädigenden Insekten.
- 35Use according to claim 34 for controlling plant-damaging insects. 35. Verwendung gemäss Anspruch 34 zur Bekämpfung von pflanzenschädigenden Insekten. 35. Verwendung gemäss Anspruch 34 zur Bekämpfung von pflanzenschädigenden saugenden Insekten.
- 36Use according to claim 35 for combating plant-damaging sucking insects. 36. Verfahren zur Bekämpfung von Insekten und Vertretem der Ordnung Akarina, dadurch gekennzeichnet, dass man die Schädlinge bzw. deren verschiedene Entwicklungsstadien und/oder ihren Aufenthaltsort mit einer pestizid wirksamen Menge einer Verbindung der Formel I gemäss Anspruch 1 oder mit einem Mittel enthaltend neben Zusatz- und Trägerstoffen eine pestizid wirksame Menge dieser Verbindung, in Kontakt bringt oder behandelt. 36. Verwendung gemäss Anspruch 35 zur Bekämpfung von pflanzenschädigenden saugenden Insekten.
- 37A method for controlling insects and representatives of the order Akarina, characterized in that the pests or their various stages of development and / or their location with a pesticidally effective amount of a compound of formula I according to claim 1 or with an agent containing in addition to and Carriers a pesticidally effective amount of this compound, in contact or treated. 37. Verfahren gemäss Anspruch 36 zur Bekämpfung von pflanzenschädigenden Insekten. 37. Verfahren zur Bekämpfung von Insekten und Vertretern der Ordnung Akarina, dadurch gekennzeichnet, dass man die Schädlinge bzw. deren verschiedene Entwicklungsstadien und/oder ihren Aufenthaltsort mit einer pestizid wirksamen Menge einer Verbindung der Formel I gemäss Anspruch 1 oder mit einem Mittel enthaltend neben Zusatz- und Trägerstoffen eine pestizid wirksame Menge dieser Verbindung, in Kontakt bringt oder behandelt.
- 38A method according to claim 37 for controlling plant-damaging insects. 38. Verfahren gemäss Anspruch 37 zur Bekämpfung von pflanzenschädigenden Insekten. 38. Verfahren gemäss Anspruch 37 zur Bekämpfung von pflanzenschädigenden saugenden Insekten.
- 39A method according to claim 38 for combating plant-damaging sucking insects. 39. Verfahren gemäss Anspruch 38 zur Bekämpfung von pflanzenschädigenden saugenden Insekten.
Independent claims39
102 paragraphs, as filed
The present invention relates to new nitroenamine derivatives, ie new 1,1-diamino-2-nitro-3-hydroxybut-1-ene derivatives, processes for their preparation, pesticides which contain these compounds and their use in the control of Pests.
These nitroenamine derivatives according to the invention correspond to the formula<chemistry id="chem0001" num="0001"><img file="EP0453398A2_D0001.tif" /></chemistry>wherein<ul id="ul0001" list-style="none"><li>R, hydrogen, C<sub>1</sub>-C<sub>6</sub>-Alkyl or C<sub>3</sub>-C<sub>6</sub>Cycloalkyl,</li><li>R<sub>2</sub> Hydrogen or C<sub>1</sub>-C<sub>6</sub>-Alkyl,</li><li>R<sub>3</sub> Hydrogen, C<sub>1</sub>-C<sub>6</sub>-Alkyl or C<sub>3</sub>-C<sub>6</sub>Cycloalkyl,</li><li>R<sub>4</sub> Hydrogen, C<sub>1</sub>-C<sub>6</sub>-Alkyl, C<sub>3</sub>-C<sub>6</sub>-Cycloalkyl or a radical -CH<sub>2</sub>-B, or R<sub>3</sub> and R<sub>4</sub> together - (CH<sub>2</sub>)<sub>4</sub>-or - (CH<sub>2</sub>)<sub>5</sub>-;</li><li>X halogen or C<sub>1</sub>-C<sub>6</sub>-Haloalkyl;</li><li>Y and Z halogen;</li><li>A is an unsubstituted or mono- to tetrasubstituted aromatic or non-aromatic, monocyclic or bicyclic heterocyclic radical, in which one or two substituents from group C<sub>l</sub>-C<sub>3</sub>-Haloalkyl, cyclopropyl, halocyclopropyl, C<sub>2</sub>-C<sub>3</sub>Alkenyl, C<sub>2</sub>-C<sub>3</sub>-Alkynyl, CrC3-haloalkenyl, C<sub>2</sub>-C<sub>3</sub>-Haloalkynyl, C<sub>1</sub>-C<sub>3</sub>-Haloalkoxy, C<sub>1</sub>-C<sub>3</sub>-Alkylthio, C<sub>1</sub>-C<sub>3</sub>-Halogenalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro and one to four substituents from group C<sub>1</sub>-C<sub>3</sub>-Alkyl, C<sub>1</sub>-C<sub>3</sub>-Alkoxy and halogen belong;</li><li>B phenyl, cyanophenyl, nitrophenyl, halophenyl with 1 to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, by one or two substituents from group C<sub>1</sub>-C<sub>3</sub>-Atky), C<sub>1</sub>-C<sub>3</sub>-Halogenalkyl, cyclopropyl, halocydopropyl, C<sub>2</sub>-C<sub>3</sub>Alkenyl, C<sub>2</sub>-C<sub>3</sub>Alkynyl, C<sub>1</sub>-C<sub>3</sub>-Alkoxy, C<sub>2</sub>-C<sub>3</sub>-Halogenalkenyl, C<sub>2</sub>-C<sub>3</sub>-Haloalkynyl, C<sub>1</sub>-C<sub>3</sub>-Haloalkoxy, C<sub>1</sub>-C<sub>3</sub>-Alkylthio, C<sub>1</sub>-C<sub>3</sub>Haloalkylthio, allyloxy, propargoxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro substituted 5-thiazolyl; or by one or two radicals from group C<sub>1</sub>-C<sub>3</sub>-Haloalkyl, cyclopropyl, halocyclopropyl, C<sub>2</sub>-C<sub>3</sub>Alkenyl, C<sub>2</sub>-C<sub>3</sub>Alkynyl, C<sub>2</sub>-C<sub>3</sub>-Halogenalkenyl, C<sub>2</sub>-C<sub>3</sub>-Haloalkynyl, C<sub>1</sub>-C<sub>3</sub>-Haloalkoxy, C<sub>1</sub>-C<sub>3</sub>-Alkylthio, C<sub>1</sub>-C<sub>3</sub>-Halogenalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyan and nitro or by one to four radicals from group C<sub>l</sub>-C<sub>3</sub>-Alkyl, C<sub>1</sub>-C<sub>3</sub>-Alkoxy or halogen substituted 3-pyridyl, and their salts with inorganic acids; where only one of the radicals R<sub>1</sub>, R<sub>3</sub> and R<sub>4 </sub>can stand for hydrogen.</li></ul>
Preferred compounds of the formula according to the invention are those in which the heterocyclic radical A is unsaturated and is bonded via one of its ring carbon atoms to the rest of the compound of the formula; those in which the heterocyclic radical A contains at least one nitrogen atom; and those in which the heterocyclic radical A contains one to three heteroatoms from the series consisting of oxygen, sulfur and nitrogen, at most one of which is an oxygen or sulfur atom.
The ring systems included in the definition of the heterocyclic radical A thus contain at least one heteroatom as a ring member, that is to say at least one of the atoms forming the underlying ring-shaped base body is different from carbon. In principle, all atoms of the periodic system of the elements are able to act as ring members, provided that they can form at least two covalent bonds. The heterocyclic radical is preferably unsaturated and bonded to the base body of the nitroenamine of the formula via a carbon atom ring member. Unsaturated ring systems of definition A thus contain one or more double bonds. Such ring systems are preferably polyunsaturated and generally have an aromatic character. Preferred are ring systems under the definition of A, in which the heterocyclic radical A contains one to three heteroatoms from the series oxygen, sulfur and nitrogen, of which one heteroatom is always nitrogen and at most one oxygen atom or sulfur atom is contained. Examples of heterocyclic radicals of the definition A according to the invention can be found in the group of basic bodies of the following structures:<chemistry id="chem0002" num="0002"><img file="EP0453398A2_D0002.tif" /></chemistry><chemistry id="chem0003" num="0003"><img file="EP0453398A2_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP0453398A2_D0004.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP0453398A2_D0005.tif" /></chemistry><chemistry id="chem0006" num="0006"><img file="EP0453398A2_D0006.tif" /></chemistry><chemistry id="chem0007" num="0007"><img file="EP0453398A2_D0007.tif" /></chemistry><chemistry id="chem0008" num="0008"><img file="EP0453398A2_D0008.tif" /></chemistry><chemistry id="chem0009" num="0009"><img file="EP0453398A2_D0009.tif" /></chemistry><chemistry id="chem0010" num="0010"><img file="EP0453398A2_D0010.tif" /></chemistry><chemistry id="chem0011" num="0011"><img file="EP0453398A2_D0011.tif" /></chemistry><chemistry id="chem0012" num="0012"><img file="EP0453398A2_D0012.tif" /></chemistry><chemistry id="chem0013" num="0013"><img file="EP0453398A2_D0013.tif" /></chemistry><chemistry id="chem0014" num="0014"><img file="EP0453398A2_D0014.tif" /></chemistry><chemistry id="chem0015" num="0015"><img file="EP0453398A2_D0015.tif" /></chemistry><chemistry id="chem0016" num="0016"><img file="EP0453398A2_D0016.tif" /></chemistry><chemistry id="chem0017" num="0017"><img file="EP0453398A2_D0017.tif" /></chemistry><chemistry id="chem0018" num="0018"><img file="EP0453398A2_D0018.tif" /></chemistry><chemistry id="chem0019" num="0019"><img file="EP0453398A2_D0019.tif" /></chemistry>where a radical is unsubstituted according to the above formulas or, depending on the substitution possibilities of the ring system in question, can carry up to four of the substituents defined under formula and E for C<sub>1</sub>-C<sub>3</sub>-Alkyl and Y for hydrogen, C<sub>1</sub>-C<sub>3</sub>-Alkyl or cyclopropyl are available. These heterocycles A are preferably unsubstituted or they carry one to three substituents from the group halogen, C.<sub>1</sub>-C<sub>3</sub>-Alkyl, C<sub>1</sub>-C<sub>3</sub>Haloalkyl, C<sub>1</sub>-C<sub>3</sub>-Haloalkoxy or C<sub>1</sub>-C<sub>3</sub>-Alkoxy. Very particularly preferred heterocycles A are pyridyl radicals or thiazolyl radicals, such as, for example, 3-pyridyl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl, 2-halothiazol-4-yl, 1-oxopyrid-3-yl , 1-oxo-2-halopyrid-5-yl, 1-oxo-2,3-dihalopyrid-5-yl.
Also to be emphasized are those compounds of the formula according to the invention which are characterized in that the radical B represents a phenyl, pyridyl or thiazolyl radical which is unsubstituted or by one or two radicals from the group halogen, C<sub>1</sub>-C<sub>3</sub>-Alkyl, C<sub>1</sub>-C<sub>3</sub>Haloalkyl, C<sub>1</sub>-C<sub>3</sub>-Haloalkoxy or C<sub>l</sub>-C<sub>3</sub>Alkoxy is substituted.
Because of their biological action, preference is given to those compounds of the formula I in which R<sub>1</sub> and R<sub>3</sub> Represent hydrogen, methyl, ethyl or cyclopropyl; where R<sub>2</sub> Means hydrogen; where R<sub>4</sub> Represents hydrogen or methyl; where R<sub>1</sub> and R<sub>3</sub> independently of one another hydrogen, methyl, ethyl or cyclopropyl, R<sub>2</sub> Hydrogen, R<sub>4</sub> Hydrogen or methyl, A pyridyl, 1-oxopyridyl, thiazolyl or in each case by one to three substituents from the group halogen, C<sub>l</sub>-C<sub>3</sub>-Alkyl, C<sub>1</sub>-C<sub>3</sub>Haloalkyl, C<sub>1</sub>-C<sub>3</sub>-Haloalkoxy or C<sub>1</sub>-C<sub>3</sub>Alkoxy substituted pyridyl, 1-oxopyridyl or thiazolyl; where X is fluorine, chlorine, bromine or C<sub>1</sub>-C<sub>3</sub>Haloalkyl having 1 to 7 fluorine atoms and Y and Z independently of one another are fluorine, chlorine or bromine, in particular X, Y and Z independently of one another being fluorine, chlorine or bromine, and in particular X, Y and Z being chlorine; where R<sub>1</sub> and R<sub>3</sub> Methyl, R<sub>2</sub> and R<sub>4</sub> Hydrogen; and X, Y and Z are independently fluorine, chlorine or bromine; wherein A is pyridyl or pyridyl substituted by one or two chlorine atoms; or wherein A is thiazolyl or thiazolyl substituted by a chlorine atom, preferably 1,3-thiazol-5-yl.
Of particular interest because of their good pesticidal properties are those compounds according to the invention of the formula wherein X is fluorine or bromine, preferably fluorine, and Y and Z are halogen, preferably fluorine or chlorine, those in which XC<sub>1</sub>-C<sub>6</sub>Haloalkyl having 4 to 13, preferably 2 to 13, halogen atoms; as well as those in which X is trifluoromethyl or one of the radicals -C<sub>2</sub>F<sub>5</sub> or -C<sub>3</sub>F<sub>7</sub> mean.
In the definition of Formula 1 according to the invention, the individual generic terms are to be understood as follows:<ul id="ul0002" list-style="none"><li>The halogen atoms which are suitable as substituents are both fluorine and chlorine and also bromine and iodine, fluorine, chlorine and bromine being preferred. Halogen is to be understood as an independent substituent or as part of a substituent as in haloalkyl, haloalkylthio, haloalkoxy, halocycloalkyl, haloalkenyl, haloalkynyl, haloallyloxy or haloallylthio. The alkyl, alkylthio, alkenyl, alkynyl and alkoxy radicals which are suitable as substituents can be straight-chain or branched. Examples of such alkyls are methyl, ethyl, propyl, isopropyl, butyl, i-butyl, sec-butyl or tert-butyl. Suitable alkoxy radicals include: methoxy, ethoxy, propoxy, isopropoxy or butoxy and their isomers. Alkylthio stands for example for methylthio, ethylthio, isopropylthio, propylthio or the isomeric butylthio. If the alkyl, alkoxy, alkenyl, alkynyl or cycloalkyl groups which are suitable as substituents are substituted by halogen, they can only be partially or also perhalogenated. The definitions given above apply to halogen, alkyl and alkoxy. Examples of the alkyl elements of these groups are methyl which is mono- to trisubstituted by fluorine, chlorine and / or bromine, for example CHF<sub>2</sub> or CF<sub>3</sub>; the one to five times substituted by fluorine, chlorine and / or bromine ethyl such as CH<sub>2</sub>CF<sub>3</sub>, CF<sub>2</sub>CF<sub>3</sub>, CF<sub>2</sub>CCI<sub>3</sub>, CF<sub>2</sub>CHCI<sub>2</sub>, CF<sub>2</sub>CHF<sub>2</sub>, CF<sub>2</sub>CFCl<sub>2</sub>, CF<sub>2</sub>CHBr<sub>2</sub>, CF<sub>2</sub>CHCIF, CF<sub>2</sub>CHBrF or CCIFCHCIF; the one to seven times substituted by fluorine, chlorine and / or bromine propyl or isopropyl such as CH<sub>2</sub>CHBrCH<sub>2</sub>Br, CF<sub>2</sub>CHFCF<sub>3</sub>, CH<sub>2</sub>CF<sub>2</sub>CF<sub>3</sub> or CH (CF<sub>3</sub>)<sub>2</sub>; butyl or one of its isomers, such as CF (CF<sub>3</sub>) CHFCF<sub>3</sub> or CH<sub>2</sub>(CF<sub>2</sub>)<sub>2</sub>CF<sub>3</sub>; 2-chlorocyclopropyl or 2,2-difluorocyclopropyl; 2,2-difluorovinyl, 2,2-dichlorovinyl, 2-chloroallyl, 2,3-dichlorovinyl or 2,3-dibromovinyl.</li></ul>
If the defined alkyl, alkoxy or cycloalkyl groups are substituted by other substituents, they can be substituted one or more times by the same or different of the substituents listed. One or two further substituents are preferably present in the substituted groups. The cycloalkyl radicals which are suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Alkenyl and alkynyl groups contain an unsaturated carbon-carbon bond. Typical representatives are allyl, methallyl or propargyl, but also vinyl and ethynyl. The double or triple bonds in allyloxy, propargyloxy, allylthio or propargylthio are preferably separated from the point of attachment to the heteroatom (O or S) by a saturated carbon atom
Heterocyclic compounds which contain a nitroenamine structure are already known as insecticides from EP-A-192 060, EP-A-302 389 and EP-A-302 833. However, the biological properties of these compounds are not fully satisfactory in pest control. Structurally, the compounds of the formula according to the invention are distinguished from the known nitroenamines mentioned above in particular by the presence of the special 3,4-substituents in the n-but-1-ene chain.
The compounds of the formula I according to the invention also include the salts with agrochemically compatible inorganic acids. Examples of such acids are hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid and nitric acid and acids with the same central atom and higher or lower oxidation levels such as perchloric acid, nitrous acid or phosphorous acid.
The compounds of the formula according to the invention can be present as double bond isomers, for example cis, trans isomers, or as stereoisomers on the carbon atom 3. The compounds of the formula I are to be understood as meaning such isomeric forms and mixtures thereof.
The compounds of formula 1 according to the invention can be prepared analogously to known processes. For example, the compound of formula I is obtained by using a 1,1-diamino-2-nitroethyl derivative of formula II<chemistry id="chem0020" num="0020"><img file="EP0453398A2_D0020.tif" /></chemistry>with a compound of formula 111<chemistry id="chem0021" num="0021"><img file="EP0453398A2_D0021.tif" /></chemistry>converts, where R, to R<sub>4</sub>, A, X, Y and Z have the meanings given above.
The process according to the invention is advantageously carried out in an inert solvent at temperatures between 0 ° C. and + 120 ° C., in particular between + 20 ° C. and + 80 ° C. Particularly suitable solvents are: Suitable solvents are, for example aromatic hydrocarbons such as benzene, toluene and xylene; Ethers such as tetrahydrofuran, dioxane and diethyl ether, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; Alcohols such as methanol, ethanol and propanol; Esters of aliphatic acids, such as ethyl acetate; aliphatic amides such as dimethylformamide and dimethylacetamide; Acetonitrile and other solvents that do not affect the reaction. These solvents can also be used as mixtures. The reaction can be carried out, in particular if the starting aldehyde compound of the formula 111 is in the hydrate form, with the addition of a dehydrating agent, such as molecular sieves, or by azeotropic removal of the water of reaction formed. It is expedient for basic conditions, ie pH values> 8 and high temperatures above about 100 ° C. should be avoided because the desired products of the formula are unstable under these reaction conditions.
The intermediates of the formulas II (1,1-diamino-2-nitroethylene derivatives) and 111 (haloacetaldehydes) are known or can be prepared in analogy to known processes (cf. EP Patent Application Nos. 302,389 and 302,833).
It has now been found that the compounds of the formula I according to the invention are valuable active compounds in pest control with favorable tolerability to warm-blooded animals, fish and plants. In particular, the use of the active compounds according to the invention relates to insects and arachnids which occur in useful and ornamental plants in agriculture, in particular in cotton, vegetable and fruit plantations, in forestry, in the protection of stored goods and materials, and in the hygiene sector, in particular in domestic and farm animals. The compounds of the formula are also suitable for seed treatment (seed dressing agents) for combating, in particular, aphids, the very low bird toxicity of the compounds being of great importance. They are effective against all or individual stages of development of normally sensitive but also resistant species. Their effect can be seen in the immediate killing of the pests or only after some time, for example when molting, or in a reduced egg deposition and / or hatching rate. The pests mentioned above include: from the order Lepidoptera, for example Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydiaeappis, diat. Spp.,. , Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scisella, Lithocoll spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris rapae, Pieris sap. Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp .; from the order Coleoptera, for example Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa Lissemtrusus spp. Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp .; from the order of the Orthoptera, for example Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp; from the order of the Isoptera, for example Reticulitermes spp .; from the order of the Psocoptera, for example Liposcelis spp .; from the order of the Anoplura, for example Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp .; from the order of the Mallophaga, for example Damalinea spp. and Trichodectes spp .; from the order of the Thysanoptera, for example Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and Scirtothrips aurantii; from the order of the Heteroptera, for example Cimexspp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorisaspp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp .; from the order of the Homoptera, for example Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Emacus Erasiosumum, Coccus hesasidum. Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium comi, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp. Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporarioriseatriza; from the order of Hymenoptera for example Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp .; from the order of the Diptera, for example Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fanniauspp., Gastrophilus spp. , Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp .; from the order of the Siphonaptera, for example Ceratophyllus spp., Xenopsylla cheopis, from the order of the Acarina, for example Acarus siro, Aceria sheldoni, Aculuslechtendali, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Chorioptes spp gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Omithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp .; and from the order of the Thysanura, for example Lepisma saccharina.
The good pesticidal activity of the compounds of the formula I according to the invention corresponds to a mortality rate of at least 50-60% of the pests mentioned.
The action of the compounds according to the invention and the compositions comprising them can be significantly broadened by adding other insecticides and / or acaricides and adapted to the given circumstances. Representatives of the following classes of active substances are, for example, possible additives: organic phosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations.
The compounds of the formula I are used in unchanged form or, preferably, together with the auxiliaries customary in formulation technology and can therefore, for example, form emulsion concentrates, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in polymeric substances are processed in a known manner. The application methods, such as spraying, atomizing, dusting, scattering or pouring, as well as the means are chosen in accordance with the intended goals and the given conditions.
The formulation, that is to say the agents, preparations or compositions containing the active ingredient of the formula or combinations of these active ingredients with other insecticides or acaricides, and optionally a solid or liquid additive, are prepared in a known manner, for example by intimately mixing and / or grinding the Active ingredients with extenders, such as solvents, solid carriers, and optionally surface-active compounds (surfactants).
Possible solvents are: Aromatic hydrocarbons, preferably fractions Cε to C<sub>12</sub>, such as xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane, paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones, such as cyclo Solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils, such as epoxidized coconut oil or soybean oil, or water.
Natural rock powders such as calcite, talc, kaolin, Montrnorillonite or attapulgite are generally used as solid carriers, for example for dusts and dispersible powders. To improve the physical properties, highly disperse silicas or highly disperse absorbent polymers can also be added. Porous types such as pumice, broken brick, sepiolite or bentonite are suitable as granular, adsorptive granule carriers, and calcite or sand are suitable as non-sorptive carrier materials. In addition, a large number of granulated materials of inorganic or organic nature, such as in particular dolomite or comminuted plant residues, can be used.
Depending on the nature of the active ingredient of the formula to be formulated or the combinations of these active ingredients with other insecticides or acaricides, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants are also to be understood as mixtures of surfactants.
Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.
Suitable soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C<sub>10</sub>-C<sub>22</sub>), such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut or tall oil. The surfactants also include the fatty acid methyl taurine salts and modified and unmodified phospholipids.
However, so-called synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are generally present as alkali, alkaline earth or optionally substituted ammonium salts and generally have an alkyl radical with 8 to 22 carbon atoms, alkyl also including the alkyl part of acyl radicals, for example the sodium or calcium Salt of lignin sulfonic acid, dodecyl sulfuric acid ester or a fatty alcohol sulfate mixture made from natural fatty acids. This subheading also includes the salts of sulfuric acid esters and sulfonic acids from fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid residue with about 8-22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a naphthalenesulfonic acid / formaldehyde condensation product. Corresponding phosphates, such as, for example, salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide adduct, are also suitable.
Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols. Other suitable nonionic surfactants are the water-soluble 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups containing polyethylene oxide adducts with polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Examples of nonionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, castor oil thioxilate, polypropylene / polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, are also suitable
The cationic surfactants are primarily quaternary ammonium salts which act as N-. Substituents contain at least one alkyl radical with 8 to 22 carbon atoms and have low, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals as further substituents. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example the stearyltrimethylammonium chloride or the benzyldi (2-chloroethyl) ethylammonium bromide.
The surfactants commonly used in formulation technology are described, for example, in the following publications:<ul id="ul0003" list-style="none"><li>"1985 International Mc Cutcheon's Emulsifiers & Detergents", Glen Rock NJ USA, 1985 ",</li><li>"H. Stache," Tensid-Taschenbuch ", 2nd edition, C. Hanser Verlag Munich, Vienna 1981,</li><li>M. and J. Ash. "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981.</li></ul>
The pesticidal preparations generally contain 0.1 to 99%, in particular 0.1 to 95% active ingredient of the formula or combinations of this active ingredient with other insecticides or acaricides, 1 to 99.9% of a solid or liquid additive and 0 to 25% , in particular 0.1 to 20%, of a surfactant. While concentrated agents are preferred as a commercial product, the end user generally uses diluted preparations which have significantly lower active substance concentrations. Typical application concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The application rates per hectare are generally 1 to 1000 g of active ingredient per hectare, preferably 25 to 500 g / ha.
In particular, preferred formulations are composed as follows (% = weight percent), a compound of the formula 1 being present as active ingredient, such as, for example, the compounds No. 1,001, 1,008, 1,009, 1,011, 1,012, 1,015, 1,028, 1,081, 1,084, 1,085, 1,101, 1,102, 1,157, 1,105, 1,109, 1,010, 1,028, 1,022:
Emulsifiable concentrates:
<tables id="tabl0001" num="0001"><img file="EP0453398A2_D0022.tif" /></tables>Dusts:<tables id="tabl0002" num="0002"><img file="EP0453398A2_D0023.tif" /></tables>Suspension concentrates:<tables id="tabl0003" num="0003"><img file="EP0453398A2_D0024.tif" /></tables>Wettable powders:<tables id="tabl0004" num="0004"><img file="EP0453398A2_D0025.tif" /></tables>Granules:<tables id="tabl0005" num="0005"><img file="EP0453398A2_D0026.tif" /></tables>
The agents can also contain other additives such as stabilizers, defoamers, preservatives, viscosity regulators, binders, adhesives and fertilizers or other active ingredients to achieve special effects.
The following examples serve to illustrate the invention. They do not limit the invention.
Example 1: Production of
1-Methylamino-1- [N- (6-chloropyrid-3-ylmethyl) -N-methyl] -2-nitro-3-hydroxy-4,4,4-trichlorobut-1-ene.
To a mixture of 2.56 g (10 mmol) of 1-methylamino-1- [N- (6-chloro-pyrid-3-ylmethyl) -N-methyl] -amino-2-nitroethylene in 30 ml of methylene chloride, 1.06 ml (10.8 mmol) chloral added. After stirring at room temperature for 2 hours, the reaction mixture is filtered and the crystals obtained are washed with a large amount of methylene chloride. 3.81 g (94%) of the title compound of the formula are obtained<chemistry id="chem0022" num="0022"><img file="EP0453398A2_D0027.tif" /></chemistry>with a melting point of 130 ° C (compound No. 1.008).
Example 2: Preparation of 1-methylamino-1- [N- (6-chloropyrid-3-ylmethyl) -N-methyl] -2-nitro-3-hydroxy-4,4-difluoro-4-chlorobut-1 -en.
7.42 g of chlorofluoroacetaldehyde are added to a mixture of 14.4 g of 1-methylamino-1- [N- (6-chloropyrid-3-ylmethyl) -N-methyl] amino-2-nitroethylene in 150 ml of methylene chloride. H<sub>2</sub>0 given. After stirring for 2 days at room temperature, the reaction mixture is filtered and the crystals obtained are washed with methylene chloride. The title compound of the following formula is obtained in an amount of 17.2 g<chemistry id="chem0023" num="0023"><img file="EP0453398A2_D0028.tif" /></chemistry>with an mp of 142-143 ° C (compound no. 1.011). Example 3: Preparation of 1-methylamino-1- (N- (6-chloropyrid-3-ylmethyl) -N-methyl] -2-nitro-3-hydroxy-4,4,5,5,6,6 , 6-heptafluoro-hex-1-ene.
To a mixture of 2.56 g of 1-methylamino-1- [N- (6-chloropyrid-3-ylmethyl) -N-methyl] -amino-2-nitroethylene and 3.24 g of heptafluorobutyraldehyde hydrate in 50 ml of methylene chloride, add 5 g molecular sieve 4 A given. After stirring for 2 days at room temperature, the reaction mixture is filtered and the filtrate is evaporated. The crystals obtained are washed with hexane / isopropanol (1: 1). 4.02 g of the title compound of the formula are obtained<chemistry id="chem0024" num="0024"><img file="EP0453398A2_D0029.tif" /></chemistry>with a melting point of 93-98 ° C (compound no. 1.012)
The compounds of the formula Ia listed in Table 1 below can be prepared in a manner analogous to that indicated above.<tables id="tabl0006" num="0006"><img file="EP0453398A2_D0030.tif" /></tables><tables id="tabl0007" num="0007"><img file="EP0453398A2_D0031.tif" /></tables><tables id="tabl0008" num="0008"><img file="EP0453398A2_D0032.tif" /></tables><tables id="tabl0009" num="0009"><img file="EP0453398A2_D0033.tif" /></tables><tables id="tabl0010" num="0010"><img file="EP0453398A2_D0034.tif" /></tables><tables id="tabl0011" num="0011"><img file="EP0453398A2_D0035.tif" /></tables><tables id="tabl0012" num="0012"><img file="EP0453398A2_D0036.tif" /></tables><tables id="tabl0013" num="0013"><img file="EP0453398A2_D0037.tif" /></tables><tables id="tabl0014" num="0014"><img file="EP0453398A2_D0038.tif" /></tables><tables id="tabl0015" num="0015"><img file="EP0453398A2_D0039.tif" /></tables><tables id="tabl0016" num="0016"><img file="EP0453398A2_D0040.tif" /></tables><tables id="tabl0017" num="0017"><img file="EP0453398A2_D0041.tif" /></tables><tables id="tabl0018" num="0018"><img file="EP0453398A2_D0042.tif" /></tables><tables id="tabl0019" num="0019"><img file="EP0453398A2_D0043.tif" /></tables><tables id="tabl0020" num="0020"><img file="EP0453398A2_D0044.tif" /></tables><tables id="tabl0021" num="0021"><img file="EP0453398A2_D0045.tif" /></tables><tables id="tabl0022" num="0022"><img file="EP0453398A2_D0046.tif" /></tables><tables id="tabl0023" num="0023"><img file="EP0453398A2_D0047.tif" /></tables><tables id="tabl0024" num="0024"><img file="EP0453398A2_D0048.tif" /></tables><tables id="tabl0025" num="0025"><img file="EP0453398A2_D0049.tif" /></tables><tables id="tabl0026" num="0026"><img file="EP0453398A2_D0050.tif" /></tables><tables id="tabl0027" num="0027"><img file="EP0453398A2_D0051.tif" /></tables><tables id="tabl0028" num="0028"><img file="EP0453398A2_D0052.tif" /></tables><tables id="tabl0029" num="0029"><img file="EP0453398A2_D0053.tif" /></tables><tables id="tabl0030" num="0030"><img file="EP0453398A2_D0054.tif" /></tables><tables id="tabl0031" num="0031"><img file="EP0453398A2_D0055.tif" /></tables><tables id="tabl0032" num="0032"><img file="EP0453398A2_D0056.tif" /></tables><tables id="tabl0033" num="0033"><img file="EP0453398A2_D0057.tif" /></tables><tables id="tabl0034" num="0034"><img file="EP0453398A2_D0058.tif" /></tables><tables id="tabl0035" num="0035"><img file="EP0453398A2_D0059.tif" /></tables><tables id="tabl0036" num="0036"><img file="EP0453398A2_D0060.tif" /></tables><tables id="tabl0037" num="0037"><img file="EP0453398A2_D0061.tif" /></tables><tables id="tabl0038" num="0038"><img file="EP0453398A2_D0062.tif" /></tables><tables id="tabl0039" num="0039"><img file="EP0453398A2_D0063.tif" /></tables><tables id="tabl0040" num="0040"><img file="EP0453398A2_D0064.tif" /></tables><tables id="tabl0041" num="0041"><img file="EP0453398A2_D0065.tif" /></tables><tables id="tabl0042" num="0042"><img file="EP0453398A2_D0066.tif" /></tables><tables id="tabl0043" num="0043"><img file="EP0453398A2_D0067.tif" /></tables><tables id="tabl0044" num="0044"><img file="EP0453398A2_D0068.tif" /></tables><tables id="tabl0045" num="0045"><img file="EP0453398A2_D0069.tif" /></tables><tables id="tabl0046" num="0046"><img file="EP0453398A2_D0070.tif" /></tables><tables id="tabl0047" num="0047"><img file="EP0453398A2_D0071.tif" /></tables><tables id="tabl0048" num="0048"><img file="EP0453398A2_D0072.tif" /></tables><tables id="tabl0049" num="0049"><img file="EP0453398A2_D0073.tif" /></tables><tables id="tabl0050" num="0050"><img file="EP0453398A2_D0074.tif" /></tables>
Example 4: (Formulations -% = weight percent)<tables id="tabl0051" num="0051"><img file="EP0453398A2_D0075.tif" /></tables>
Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.<tables id="tabl0052" num="0052"><img file="EP0453398A2_D0076.tif" /></tables>
The solutions are suitable for use in the form of tiny drops.<tables id="tabl0053" num="0053"><img file="EP0453398A2_D0077.tif" /></tables>
The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated off in vacuo.<tables id="tabl0054" num="0054"><img file="EP0453398A2_D0078.tif" /></tables>
Ready-to-use dusts are obtained by intimately mixing the carrier substances with the active ingredient.<tables id="tabl0055" num="0055"><img file="EP0453398A2_D0079.tif" /></tables>
The active ingredient or combination of active ingredients is mixed with the additives and ground well in a suitable mill. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.
Example 4.6: Emulsion concentrate
<tables id="tabl0056" num="0056"><img file="EP0453398A2_D0080.tif" /></tables>
Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.<tables id="tabl0057" num="0057"><img file="EP0453398A2_D0081.tif" /></tables>
Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding it in a suitable mill.
Example 4.8: Extruder granules
<tables id="tabl0058" num="0058"><img file="EP0453398A2_D0082.tif" /></tables>
The active ingredient or combination of active ingredients is mixed with the additives, ground and moistened with water. This mixture is extruded, granulated and then dried in an air stream.
Example 4.9: Coating granules
<tables id="tabl0059" num="0059"><img file="EP0453398A2_D0083.tif" /></tables>
The finely ground active ingredient or combination of active ingredients is applied evenly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.
Example 4.10: Suspension concentrate
<tables id="tabl0060" num="0060"><img file="EP0453398A2_D0084.tif" /></tables>
The finely ground active ingredient or combination of active ingredients is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
Example 5: Action against Nilaparvata lugens
Rice plants are treated with an aqueous emulsion spray mixture which contains 400 ppm of the active ingredient. After the spray coating has dried on, the rice plants are colonized with 2nd and 3rd stage cicada larvae. Evaluation takes place 21 days later. The percentage reduction in the population (% action) is determined by comparing the number of surviving cicadas on the treated plants with those on the untreated plants.
The compounds of Table 1 show a good activity against Nilaparvata lugens in this test. In particular, the connections 1,001, 1,008, 1,009, 1,010, 1,011, 1,012, 1,015, 1,022, 1,024, 1,025, 1,028, 1,039, 1,081, 1,085, 1,101, 1,102, 1,103, 1,149, 1,153,1,157,1,165,1,169, 1,183 and 1,189 show an effect of over 80%.
Example 6: Action against Nephotettix cincticeps
Rice plants are treated with an aqueous emulsion spray mixture which contains 400 ppm of the active ingredient. After the spray coating has dried on, the rice plants are colonized with 2nd and 3rd stage cicada larvae. Evaluation takes place 21 days later. The percentage reduction in the population (% action) is determined by comparing the number of surviving cicadas on the treated plants with those on the untreated plants.
The compounds of Table 1 show good activity against Nephotettix cincticeps in this test. In particular, the connections 1,001, 1,008, 1,009, 1,010, 1,011, 1,012, 1,015, 1,022, 1,024, 1,025, 1,028, 1,039, 1,081, 1,085, 1,101, 1,102, 1,103, 1,149, 1,153, 1,157, 1,165, 1,169, 1,183 and 1,184 show an effect of over 80%.
Example 7: Activity against Spodoptera littoralis caterpillars
Young soybean plants are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active ingredient. After the spray coating has dried on, the soy plants are populated with 10 caterpillars of the third stage of Spodoptera littoralis and placed in a plastic container. Evaluation is carried out 3 days later. By comparing the number of dead caterpillars and the feeding damage on the treated plants to those on the untreated plants, the percentage reduction in the population or determines the percentage reduction in feeding damage (% effect).
The compounds of Table 1 show a good activity against Spodoptera littoralis in this test. Compound 1.015 in particular shows an effect of over 80%.
Example 8: Action against Aphis craccivora
Pea seedlings are infected with Aphis craccivora and then sprayed with a spray mixture containing 400 ppm of the active ingredient and incubated at 20 ° C. Evaluation is carried out 3 and 6 days later. The percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants.
The compounds of Table 1 show good activity against Aphis craccivora in this test. In particular, the compounds 1.008, 1.010, 1.011, 1.012, 1.015, 1.022, 1.028, 1.081, 1.084, 1.085, 1.101, 1.157, 1.165 and 1.169 show an activity of over 80%.
Example 9: Systemic action against Nilaparvata lugens
Pots of rice plants are placed in an aqueous emulsion solution containing 400 ppm of the active ingredient. The rice plants are then populated with 2nd and 3rd stage larvae. Evaluation takes place 6 days later. The percentage reduction in the population (% action) is determined by comparing the number of leafhoppers on the treated plants with those on the untreated plants.
The compounds of Table 1 show a good activity against Nilaparvata lugens in this test. In particular, the connections 1,001, 1,008, 1,010, 1,011, 1,012, 1,015, 1,022, 1,024, 1,025, 1,028, 1,039, 1,081, 1,084, 1,085, 1,101, 1,102, 1,103, 1,149, 1,153, 1,157, 1,165, 1,169, 1,183 and 1,184 show an effect above 80% even at a concentration of 12.5 ppm.
Example 10: Systemic activity against Nephotettix cincticeps
Pots of rice plants are placed in an aqueous emulsion solution containing 400 ppm of the active ingredient. The rice plants are then populated with 2nd and 3rd stage larvae. Evaluation takes place 6 days later. The percentage reduction in the population (% action) is determined by comparing the number of leafhoppers on the treated plants with those on the untreated plants.
The compounds of Table 1 show good activity against Nephotettix cincticeps in this test. In particular, the connections 1.008, 1.010, 1.011, 1.012, 1.015, 1.022, 1.024, 1.025, 1.028, 1.039, 1.081, 1.084, 1.085, 1.101, 1.102, 1.103, 1.149, 1.153, 1.157, 1.165,1.169,1.183 and 1.184 show one Effect of over 80%.
Example 11: Systemic action against Myzus persicae
Pea seedlings are infected with Myzus persicae, then with the roots in a spray mixture that <sub>4</sub>00 Contains ppm of the active ingredient, placed and incubated at 20 ° C. Evaluation is carried out 3 and 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants.
The compounds of Table 1 show a good activity against Myzus persicae in this test. In particular, the compounds 1.008, 1.010.1.011.1.012.1.015.1.028.1.081,1.084.1.085, 1.101, 1.149, 1.153, 1.157, 1.165 and 1.169 show an effect of over 80%.
Example 12: Action against Anthonomus grandis adults
Young cotton plants are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active ingredient. After the spray coating has dried on, the cotton plants are populated with 10 adults from Anthonomus grandis and placed in a plastic container. Evaluation is carried out 3 days later. By comparing the number of dead beetles and the damage caused by feeding on the treated plants to those on the untreated plants, the percentage reduction in the population or determines the percentage reduction in feeding damage (% effect).
The compounds of Table 1 show a good activity against Anthonomus grandis in this test. Compounds 1,008,1,010, 1,011, 1,012, 1,015, 1,022, 1,028, 1,101,1,149 and 1,153 in particular show an activity of over 80%.
Example 13: Action against Bemisia tabaci
Bush bean plants are placed in gauze cages and populated with adults from Bemisia tabaci (white fly). After laying eggs, all adults are removed and 10 days later the plants with the nymphs on them are sprayed with an aqueous emulsion of the active ingredients to be tested (concentration 400 ppm ) treated The evaluation takes place 14 days after the active substance application for% hatching in comparison to the untreated control batches.
The compounds according to Table 1 show good activity against Bemisia tabaci in this test. In particular, the compounds 1,011,1,012,1,015,1,081,1.084,1.085,1.101 and 1.102 show an activity of over 80%.
Example 14: Action against Diabrotica balteata larvae
Corn seedlings are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active ingredient. After the spray coating has dried on, the maize seedlings are populated with 10 second-stage larvae of Diabrotica balteata and placed in a plastic container. Evaluation is carried out 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of dead larvae on the treated plants with those on the untreated plants.
The compounds of Table 1 show good activity against Diabrotica balteata in this test. Compounds 1.010, 1.012 and 1.015 in particular show an activity of over 80%.
Example 15: Activity against Heliothis virescens caterpillars
Young soybean plants are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active ingredient. After the spray coating has dried on, the soy plants are populated with 10 caterpillars of the first stage of Heliothis virescens and placed in a plastic container. Evaluation takes place 6 days later. By comparing the number of dead caterpillars and the damage caused by feeding on the treated plants to those on the untreated plants, the percentage reduction in the population or determines the percentage reduction in feeding damage (% effect).
The compounds of Table 1 show a good activity against Heliothis virescens in this test. Compounds 1.010, 1.011 and 1.015 in particular show an activity of over 80%.
Example 16: Activity against Crocidolomia binotalis caterpillars
Young cabbages are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active ingredient. After the spray coating has dried on, the cabbages are populated with 10 caterpillars of the third stage of Crocidolomia binotalis and placed in a plastic container. Evaluation is carried out 3 days later. By comparing the number of dead caterpillars and the damage caused by feeding on the treated plants to those on the untreated plants, the percentage reduction in the population or the percentage reduction in feeding damage (% action) is determined.
The compounds of Table 1 show a good effect in this test. Compound 1.015 in particular shows an effect of over 80%.
Example 17: Action against Myzus persicae
Pea seedlings are infected with Myzus persicae and then sprayed with a spray broth containing 400 ppm of the active ingredient and incubated at 20 ° C. Evaluation is carried out 3 and 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants.
The compounds of Table 1 show a good effect in this test. Compounds 1,008, 1,010, 1,012, 1,015, 1,022 and 1,157 in particular show an activity of over 80%.
174 sheets
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Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| EP0302389B1 | Cites | European Patent Office (EPO) | Search report |
| EP0302833A2 | Cites | European Patent Office (EPO) | Search report |
| EP0392560A2 | Cites | European Patent Office (EPO) | Search report |
57 members in 30 offices
Priority claims10
| Document | Office | Kind | Date |
|---|---|---|---|
| 116990 | Switzerland | – | |
| 116990 | Switzerland | A | |
| 116990 | Switzerland | A | |
| 348190 | Switzerland | – | |
| 348190 | Switzerland | A | |
| 348190 | Switzerland | A | |
| 116990 | – | – | – |
| 348190 | – | – | – |
| CH19900001169 | – | – | – |
| CH19900003481 | – | – | – |
Members57
| Document | Office | Kind | |
|---|---|---|---|
| CA2039779A1 | Canada | A1 | |
| IE911142A1 | Ireland | A1 | |
| CN1055356A | China | A | |
| EP0453398A2This record | European Patent Office (EPO) | A2 | |
| AU7409191A | Australia | A | |
| HUT56810A | Hungary | A | |
| BR9101372A | Brazil | A | |
| KR910018356A | Republic of Korea | A | |
| ZA912532B | South Africa | B | |
| HU913452D0 | Hungary | D0 | |
| PT97265A | Portugal | A | |
| CA2054614A1 | Canada | A1 | |
| EP0484279A2 | European Patent Office (EPO) | A2 | |
| CS329291A3 | Czechoslovakia (until 1993) | A3 | |
| EP0453398A3 | European Patent Office (EPO) | A3 | |
| IE913842A1 | Ireland | A1 | |
| HUT59283A | Hungary | A | |
| IL97680D0 | Israel | D0 | |
| MX9101874A | Mexico | A | |
| EP0484279A3 | European Patent Office (EPO) | A3 | |
| ZA918703B | South Africa | B | |
| AU8696091A | Australia | A | |
| JPH04234848A | Japan | A | |
| TR25776A | Türkiye | A | |
| AU640999B2 | Australia | B2 | |
| NZ240426A | New Zealand | A | |
| YU60991A | Yugoslavia, later Serbia and Montenegro (until 2006) | A | |
| AU652000B2 | Australia | B2 | |
| NZ237681A | New Zealand | A | |
| HU209696B | Hungary | B | |
| US5407934A | United States of America | A | |
| LTIP1505A | Lithuania | A | |
| EG19474A | Egypt | A | |
| CZ279824B6 | Czechia | B6 | |
| LV10745A | Latvia | A | |
| MD255B1 | Republic of Moldova | B1 | |
| RU2043717C1 | Russian Federation | C1 | |
| EP0683980A2 | European Patent Office (EPO) | A2 | |
| MD255C2 | Republic of Moldova | C2 | |
| EE9400350A | Estonia | A | |
| LT3728B | Lithuania | B | |
| EP0484279B1 | European Patent Office (EPO) | B1 | |
| AT134478T | Austria | T | |
| ATE134478T1 | Austria | T1 | |
| DK0484279T3 | Denmark | T3 | |
| DE59107460D1 | Germany | D1 | |
| LV10745B | Latvia | B | |
| EP0683980A3 | European Patent Office (EPO) | A3 | |
| ES2084140T3 | Spain | T3 | |
| US5521195A | United States of America | A | |
| GR3019150T3 | Greece | T3 | |
| EP0683980B1 | European Patent Office (EPO) | B1 | |
| AT177902T | Austria | T | |
| ATE177902T1 | Austria | T1 | |
| DE59109117D1 | Germany | D1 | |
| ES2130479T3 | Spain | T3 | |
| GR3030226T3 | Greece | T3 |
7 legal events, as the office reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | |
|---|---|---|
| Application deemed to be withdrawnWithdrawn18D | 18D | |
| Information on the status of an ep patent application or granted ep patentGrantedSTAA | STAA | |
| Designated contracting states:AK | AK | |
| Search report despatchedPUAL | PUAL | |
| Request for examination filed17P | 17P | |
| Designated contracting states:AK | AK | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phasePUAI | PUAI |
Numbers
- Publication
- 0453398
- Publication, DOCDB
- 0453398
- Publication, EPODOC
- EP0453398
- Application
- 91810225
- Application, DOCDB
- 91810225
- Application, EPODOC
- EP19910810225
Titles3
- German
- Nitroenamin-Derivate als Schädlingbekämpfungsmittel
- English
- Nitroenamine derivatives as pesticides
- French
- Dérivés de nitroénamine comme pesticides
Classification
- CPC, 7
- C07D277/32
- C07D213/54
- A01N43/40
- A01N43/78
- C07D213/38
- C07D213/61
- C07D213/89
- IPC, 51
- A01N43 10
- A01N43 36
- A01N43 40
- A01N43 50
- A01N43 54
- A01N43 56
- A01N43 08
- A01N43 58
- A01N43 60
- A01N43 64
- A01N43 647
- A01N43 707
- A01N43 713
- A01N43 72
- A01N43 76
- A01N43 78
- A01N43 80
- A01N43 82
- A01N43 84
- A01N43 86
- A01N43 88
- A01N43 90
- C07D207 335
- C07D213 38
- C07D213 61
- C07D213 89
- C07D233 70
- C07D233 84
- C07D237 12
- C07D239 30
- C07D241 16
- C07D251 34
- C07D261 08
- C07D263 32
- C07D265 06
- C07D265 30
- C07D265 32
- C07D271 04
- C07D271 06
- C07D271 08
- C07D273 00
- C07D273 04
- C07D277 20
- C07D277 32
- C07D279 06
- C07D279 12
- C07D285 04
- C07D285 06
- C07D285 08
- C07D285 16
- C07D285 34
Designated states13
- Contracting states, 13
- Austria
- Belgium
- Switzerland
- Germany
- Denmark
- Spain
- France
- United Kingdom
- Greece
- Italy
- Liechtenstein
- Luxembourg
- Netherlands (Kingdom of the)